Azo dyestuffs



Patented Feb. 2, 1943 DYESTUFFS Neil Mitchill Mackenzie, Bound Brook, N. J., as-

signor to American Cyanamid Company, Ne York, N. Y., a corporation of Maine 7 No Drawing.

Application June 7, 1941,

Serial No. 397,085

7 Claims.

This invention relates to azo dyes prepared from sulfonic acid and sulfonamide derivatives of acetoacetic amides and may be represented by the following formula:

in which R. is an aromatic radical, R is a hydrocarbon radical of the benzene, aliphatic or alicyclic series, X is a radical included in the group consisting of SOsH, SO2NH2 and their salts, and n and n are integers in the group consisting of 1 and 2.

In the past azo dyes have been derived from sulfonic acid derivatives of acetoacetic arylides but a wider range of dyes and a much improved process of preparation is possible by the use of the intermediates employed in this invention, these intermediates being prepared by reacting diketene with amino sulfonic acids and amino sulfonamides.

In my copending application Serial No. 397,086 filed June 7; 1941, I have described compounds represented by the formula:

(CHsCOCHzC 1 ONE) nRXn pounds are coupled with diazo compounds to give new and useful azo dyes.

Many coupling components are suitable to be used in producing the dyes of this invention and among the preferred ones are the products of the reaction of diketene with the following sulfonic acids: taurine, 1-amino-propane-2-sulfonic acid, 2-amino-2-methyl-propane sulfonic acid, aminocyclohexane sulfom'c acids, benzylamine sulfonic acids, orthanilic acid, metanilic acid, sulfanilic acid, 4-amino-3-methyl-benzene sulfonic acid,

and 2-amino-5-methylabenzene sulfonic acid. Other suitable coupling components are reaction products of diamino sulfonic acids such as of phenylene diamine sulfonic acid and diaminedisulfom'c acids such as benzidine-2,2'-disulfoni'c acid. In addition mono amino dlsulfonic acids such as aniline 2,5-disulfonic acid maybereacted with diketene and the resulting products used for making the azo dyes of this invention. The -'--coup1ing component may contain 'sulfam'ide groups instead of sulfonic acid groups and acetoacetyl sulfanilamide and acetoacetyl metanilamide may be combined with diazo compounds to give useful azo dyes.

Aromatic amines may be used as suitable dia'zo components. Examples of such are unsubstituted aromatic amines such as aniline and the naphthylamines and their homologues such as the tolui'dines and the xylidines and also substitution products containing groups such as nitro, sulfonic, hydroxyl, carboxylic, halogen, nitrile, sul fonamide and acylamino. Aromatic diamines are important and also tetrazo components such as benzidine 4,4"-diamino diphenylurea, 4,4- diamino stilbene and their substitutionproducts. Some of the dyes of this invention which have a diazo component that has a metallizable group such as a hydroxyl, methoxyl, amino or carboxylicgroup in the position ortho to the amino group may be converted into valuable metal complexes, particularly the chromium or copper complexes. These dyes may also be used in the metachrome or the top chrome processes. No metallized dyes are specifically claimed in the present invention, but are claimed in the inventors copending application Serial No. 397,084, filed June 7, 1941. v I

The dyes of this invention have various uses many of those having substantive groups being applicable as dyes for vegetable or animal fibers.

The shades of thedyesproduced by this invention will vary according to the intermediates used and in the caseio'f'the'metallized dyes with the metal compoundsemployed, although the shades of the dyes are mostly in the yellow or orange range.

The inventionis illustrated but not limited-by are weight.

the following examples, in which the parts-given "Example 1 6.1 parts of dianisidine are tetrazot'ized in the usual manner with 132. parts of 38% hydro.-

chloric "acid, 40 parts of :water and 8.7 parts of 40%- sodium nitrite solution. This solution is then added to a; solution of'r1'4.1 parts 'of l-ace'toac'etylaminobenz'ene 'sulfonic 'acid and 10 parts of sodium jcarbonate'in .200 parts of water. The mixture is 'stirredidurin-g the addition and cooled The formula of this new dye in the free acid 3 NH-O-smH O OH:

Example 2 A hot solution of 6.91 parts of p-nitraniline in 19.0 parts of 38% hydrochloric acid and 50 parts of water is cooled by the addition of 250 parts of ice and diazotized in the usual manner with 34.5 parts of sodium nitrite solution. In a separate container 30.0 parts of crystalline sodium acetate are dissolved in 100 parts of a solution containing 14.1 parts of 3-acetoacetylaminobenzene sulfonic acid. The above diazo solution is added to this solution while the solution is stirred and cooled with ice. Coupling takes place rapidly and the dye separates as a yellow precipitate. On heating to the boil, the dye becomes crystalline (pale yellow needles). After cooling it is filtered off and dried. The formula of this new dye in the free acid form is:

S0 13. CO

It dyes wool from an acid bath yellow shades.

Example 3 7.65 parts of 2-carboxy-4-aminphenol are dissolved in a solution of 2.0 parts 01 sodium hydroxide in 100 parts of water. This solution is acidified by the addition of 12.2 parts of 38% hydrochloric acid and is diazotized in the usual manner with a solution of 3.45 parts of sodium nitrite in 50 parts of water. Then in a separate vessel 10.0 parts of sodium carbonate are dissolved in a solution of 14.1 parts of 3-acetoacetyl- :amino benzene sulfonic acid in 150 parts of water. The above diazo solution is then run in and stirred until the diazo has all reacted and the dye is precipitated in crystalline form (yellow needles). The dye is filtered off and dried. In the free acid form it has the following formula:

(IIONH HO- N=NCH l S 03H CO COOH I The new product dyes wool from an acid bath bright greenish yellow shades. When dyed on wool by the topchrome or metachrome method, it gives a bright reddish yellow shade of excellent fastness to washing and fulling.

Example 4 .is formed. The dye is then precipitated by the addition of common salt, converted to the crystalline fonn (yellow plates) by heating to 70 C., cooled and filtered oil. This new dye in the free acid form has the formula shown below:

CIEONHOS our to coon 1 It dyes wool by the topchrome or metachrome process very greenish yellow shades of excellent fastness to light, washing and fulling.

Example 5 A finely divided suspension of 4.73 parts of 2- amino-4-sulfophenol in 50 parts of water and 5.29 parts of 38% hydrochloric acid is diazotized in the usual manner with a solution of 1.73 parts of sodium nitrite in 25parts of water. In a separate vessel 5.0 parts of sodium carbonate are dissolved in a solution of 7.65 parts of 3-acetoacetylamino benzene sulfonic acid in 100 parts of water. The diazo solution prepared as described above is run in rapidly and the solution is stirred until coupling is complete. The dye is treated with salt at 100 C. and on cooling the dye separates as a crystalline precipitate (fine needies). It is filtered off and dried.

This new dye in the form of the free acid has the formula shown below:

| CONH It dyes wool yellow shades which become redder on after-chroming.

By the procedure outlined in this example 2- amino-4-sulfophenol can be coupled with 4- acetoacetylamino benzene sulfonic acid and with 3-methyl-4-acetoacetylamino benzene sulfonic acid to produce new azo dyes.

Example 6 3.08 parts of 2-amino-4-nitrophenol are dissolved in 3.85 parts of 38% hydrochloric acid and 45 parts of water. This solution is then diazotized with a solution of 1.38 parts of sodium nitrite in 20 parts of water. At the same time, 'a. solution is made by dissolving 7.41 parts of 1- acetoacetylaminobenzene-2,5-disulfonic acid and 6.00 parts of crystalline sodium acetate in Parts of water.

The above solution is run in rapidly and the mixture is then neutralized b adding a solution of 1.7 parts of sodium carbonate-in 17 parts of water. It is then stirred until the diazo hascompletely reacted. The dye partially precipitates in crystalline form (yellow needles). After heating to 60 C. the dye is completely precipitated by the addition of common salt. The mixture is then cooled to 40 C. and the dye is filtered off. The new product in thefree acid form has the following formula:

OH (DONE N=NCH I SOaH COCHE It dyes wool from an acid bath bright reddish yellow shades. When dyed by the topchrome or metachrome method, brownish yellow shades are obtained.

2-amino-4-nitrophenol can be coupled in a similar manner to 4-acetoacetylaminobenzene sulfonic acid and to 3-acetoacetylaminobenzene sulfonic acid.

Example 7 1.68 parts of 2-aminol-methyl-S-nitrophenol and 0.69 part of sodium nitrite are dissolved in a solution of 0.41 part of sodium hydroxide in 30 parts of water. This solution is then added during stirring and cooling to 11.0 parts of 17% hydrochloric acid and the mixture is stirred until the diazotization is complete. The diazo solution is then added to a solution of 3.25 parts of 3- methyl-4-acetoacetylaminobenzene sulfonic acid and 5.0 parts of sodium carbonate in 60 parts of water. The solution is then stirred until the coupling is complete. The dye formed separates out in the form of a brown-red gelatinous .precipitate. The slurry is then trwtedgwith common salt, heated to the boil and after cooling the precipitate of dye is filtered off. The structural formula of this new product in the free acid form is shown in the following formula:

OzN OH I l ([JONH solH N=NCH EwampleS 2.25 parts of the hydrobromide of 2-amino-4- chlorophenol are dissolved in 25 parts of water and 1.06 parts of 38% hydrochloric acid. This solution is diazotized in the conventional manner with a solution of 0.69 part of sodium nitrite in 10 parts of water. This diazo solution is then added rapidly to a solution of 2.5? parts of 3- acetoacetylaminobenzene sulfonic acid and 1.5 parts of sodium carbonate in 25 parts of water. Coupling takes place rap-idly and the dye is precipitated in crystalline form (reddish-yellow needles). The mixture is then heated to 90 C. and after cooling, the precipitate of dye is filtered ofl. Its chemical structure in the free acid state can be best represented by the following formula:

S 03H C CH3 C1 Example 9 4.68 parts of 2-amino-4-nitro-6-sulfo,phenol are dissolved in 20 parts of water and 5.15 parts of 38% hydrochloric acid solution. It is then diazotized'in the usualmanner :by adding a solution of 1.38 parts of sodium nitrite in 20 parts of water. In another vessel 5.65 parts of 3-acetoacetylaminobenzene sulfonic acid and 10 parts of sodium acetate are dissolved in 100 parts of water. The above diazo solution is then run in very slowly. During the addition of the diazo solution 10% sodium carbonate solution is added as necessary to hold the pH at about 7. After all the diazo solution is added, the mixture is stirred until the coupling is complete. The dye is then almost entirely precipitated in a reddish-yellow form. The mixture is heated to 70 C. and the new dyestufi is precipitated with common salt. The crystalline precipitate (reddish-yellow needles) is then filtered oiT at C. and dried. The formula of this new product in the free acid form is shown below:

\ $ONH N=NCH I SOaH COCHa OzN It dyes wool from an acid bath bright yellowish orange shades, which upon after-chroming become golden orange.

If an equivalent amount of 3-acetoacetylaminobenzene sulfonamide (5.63 parts) is substituted in the above example for 3-acetoacetylaminobenzene sulfonic acid, a similar dyestufl isobtained in the form of a reddish-yellow precipitate. It is isolated in the usual manner. The structure of this dyestuff in the free acid form is represented in the following formula:

H0 8 OH $ONH I SOzNH I C 0 CH OzN Example 10 5.00 parts of the diazo oxide of 1-amino-2- hydroxynaphthalenel-s-ulfonic acid are added to a solution of 5.65 parts of 4-acetoacetylaniinobenzene sulfonic acid and 4.0 parts of sodium carbonate in '75 parts of Water. The mixture is stirred until all the diazo has reacted. The dye formed is partially precipitated from the solution. The mixture is then diluted with 125 parts of water, precipitated by the addition of common salt,'and the crystalline precipitate (yellowishformula (IDONHGSOQH It dyes Wool from an acid bath yellow shades.

l-amino-Z-hydroxy naphthalenel-sulfonic acid can be coupled with B-acetoacetylaminobenzene sulfonic acid and 3-acetoacetylamino-4-chlorbenzene sulfonic acid, and dyes having similar properties are obtained.

Example 11 13.7 parts anthranilic acid are dissolved in 14.5 parts of 38% hydrochloric acid and 200 parts of water. This solution is diazotized in the known manner with 6.9 parts of sodium nitrite. new product which in the form of the free acid This diazo solution is then added in the preshas the following formula: ence of ice to a solution of 25.6 parts of bis-4,4- acetoacetyl-benzidine-2,2-disulfonic acid and 20 OH 1 coNncmcmsoan parts of solium carbonate in 700 parts of water. 5 Coupling takes place rapidly and a granular yellow precipitate of dye is formed. It is filtered 00cm off and dried. This new dye, which in the form 1130' of the free acid is represented by the following dyes Wool yellow tints which become redder upon formula: after treatment with chromium salts.

Hoo coon N=NCH 00cm I 80311 SOsH COCHa dyes wool from an acid bath yellow tints. What I claim is:

1. As new products, azo dyes having the fol- Easample 12 lowing formula:

1 o0oH, 3.08 parts of 2-amino-4-nitropheno1 are dissolved in 3.85 parts of 38% hydrochloric acid and 45 parts of water. This solution is then diazo- (NJ-NH tized in the usual manner with 1.38 parts of so- 111 whlqh R i an aromatic di a R is a radical dium nitrite. The diazo solution so obtained is belQnglng t0 the group C t g of hydrocarbon then added to a solution of 4.88 parts of acetoacradwals of the benzene. h nyl. l wer alkylene.

aralkyl and alicyclic series, X is a radical included in the group consisting of SOaH, and its salts, n is an integer included in the group consisting of 1 and 2, and n is an integer included in the group etyl-amino-methane sulfonic acid and 5.0 parts of sodium acetate in 100 parts of water. The

mixture is neutralized by the addition of dilute sodium carbonate solution and then stirred at 40 C. until the coupling is complete. The new dyetlng of 1, 2 and 3.

stufi, which separates in crystalline form (orange New P c s n accordance with claim 1 in needles) is filtered off and dried. The new Whwh 1s e y ene.

product, which in the form f the free acid has 3 New products in accordance with claim 1 in the following f rmula: which R is a radical of the benzene series, havmg a hydroxyl or a carboxyl group ortho to the OH azo group.

1 (BON 2 4. New products in accordance with claim 1 in N=NCH which R is a radical of the benzene series, hav- COCHK ing a hydroxyl group ortho to the azo group and being further substituted by at least one nitro group.

dyes wool from an acid bath reddish yellow 5.The compound having the following formula:

shades. When dyed on wool by the topchrome OH or metachrome process, golden yellow shades I CONH.CH2.CH2SO3H having good fastness properties are obtained. Q

I Example 13 S031; CO GH A finely divided suspension of 4.73 parts of 2- The compound havmg the fonnula amino-i-sulfophenol in 50 parts of water and R CONE 5.76 parts of 38% hydrochloric acid is diazotized in the known manner with 1.73 parts of sodium s O H nitrite. The diazo solution obtained is added to 00011, a a solution of 6.2? parts of acetoacetyl-aminoethane sulfonic acid and 8.5 parts of sodium car- The compound having e f rmula: bonate in 150 parts of Water. The mixture is 01 then stirred until the coupling is complete. The (IJONH mixture is then neutralized with dilute hydrochloric acid and the dye is precipitated in the Q 6 O CH SOSH form of yellow needles by the addition of com- 01 3 mon salt. The dye is filtered off and dried. The NEIL MITCHILL MACKENZIE. 

